ChemInform Abstract: Refined Crystal Structure and Idealized Structure of Mixed‐Valent Eu4F5(CN2)2: Transition Possible.

The title compound is prepared by solid state reaction of EuF₃, EuF_2+x, and Li₂(CN₂) at 700 °C and characterized by single crystal XRD, ¹⁵¹Eu Moessbauer spectroscopy, and magnetic measurements.     

Synthesis and crystal and molecular structure of mixed-ligand compounds Eu(S2CN(C2H5)2)3(2,2′-Bipy) and Eu(S2CN(C2H5)2)3(1,10-Phen)

Synthetic procedures were developed and X-ray diffraction analysis was performed for two mixed-ligand compounds of europium(III) with diethyldithiocarbamate ions and 2,2′-bipyridyl (2,2′-Bipy) or 1,10-phenanthroline (Phen): Eu(S₂CN(C₂H₅)₂)₃(2,2′-Bipy) (I) and Eu(S₂CN(C₂H₅)₂)₃Phen (II). The structures of the complexes consist of discrete monomer molecules; the coordination polyhedron of Eu (EuN₂S₆ is a node) is a distorted dodecahedron. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 2, pp. 300–309, March–April, 1997.     

The crystal structure of (AsPh4)2[OsN(OH)(CN)4]

Summary The crystal structure of (AsPh₄)₂[OsN(OH)(CN)₄] has been determined from three-dimensional X-ray diffraction data. The [OsN(OH)(CN)₄]^2– ion has a distorted octahedral geometry with bond distances: ON = 1.606(5), Os-OH = 2.123(5) and Os-C_av = 2.068(8) Å. The osmium atom is displaced 0.26 Å from the equatorial cyano-carbon atom plane.     

Homoleptic selenium cyanides: attempted preparation of Se(CN)4 and redetermination of the crystal structure of Se(CN)2

The preparation of Se(CN) 4 was attempted by the reaction of SeF 4 with Me 3SiCN at low temperatures. However, selenium tetracyanide could not be detected by NMR spectroscopy; instead, the decomposition product Se(CN) 2 was isolated and its crystal structure was redetermined. In the structure of Se(CN) 2, layers are present with secondary Se...N interactions. The structure of Se(CN) 4 and its reductive decomposition reaction has been calculated at the MP2 level of theory.     

K3Eu5(PO4)6: hydrothermal synthesis,crystal structure and photoluminescence properties

An anhydrous orthophosphate, K₃Eu₅(PO₄)₆ (tripotassium pentaeuropium hexaphosphate), has been prepared by a high‐temperature solid‐state reaction combined with hydrothermal synthesis, and its crystal structure was determined by single‐crystal X‐ray diffraction analysis (SC‐XRD). The results show that the compound crystallizes in the monoclinic space group C2/c and the structure features a three‐dimensional framework of [Eu₅(PO₄)₆]_∞, with the tunnel filled by K⁺ ions. The IR spectrum, UV–Vis spectrum and luminescence properties of polycrystalline samples of K₃Eu₅(PO₄)₆, annealed at temperatures of 650, 700, 750, 800 and 850 °C, were investigated. Although with a full Eu³⁺ concentration (9.96 × 10²¹ ions cm^?3), the self‐activated phosphor K₃Eu₅(PO₄)₆ shows s strong luminescence emission intensity with a quantum yield of 37%. Under near‐UV light excitation (393 nm), the series of samples shows the characteristic emissions of Eu³⁺ ions in the visible region from 575 to 715 nm. The sample sintered at 800 °C gives the strongest emission and its lifetime sintered at 800 °C (1.88 ms) is also the longest of all.     

The crystal structure of caesium tetracyanodioxoosmate(VI) Cs2[OsO2(CN)4]

Summary The crystal structure of the caesium salt of [OsO₂(CN)₄]^2– has been determined from three-dimensional x-ray diffraction data. The orange crystals are monoclinic, space group C2/m with a=12.125(2), b=8.284(1), c=5.457(1) Å, =102.01(1)° with two molecules per unit cell. The final R value using 778 observed reflections and anisotropic thermal parameters for all atoms was 0.028. The [OsO₂(CN)₄]^2– ion has an octahedral geometry. Bond distances: Os=O=1.750(8)Å and Os–C=2.093(9)Å.     

Synthese von Y2O2(CN2) und Leuchtstoffeigenschaften von Y2O2(CN2):Eu

Synthesis of Y₂O₂(CN₂) and Luminescence Properties of Y₂O₂(CN₂):Eu Crystalline powders of the new compound Y₂O₂(CN₂) were prepared by solid state reactions from different mixtures of YCl₃/YOCl/Y₂O₃ and Li₂(CN₂) at temperatures between 620 °C and 650 °C. Structure refinements based on X‐ray powder diffraction revealed that trigonal Y₂O₂(CN₂) crystallizes with a structure that is closely related to that of Y₂O₂S, whereas linear N‐C‐N units replace sulphur atoms in Y₂O₂S. In addition, a hexagonal polytype of Y₂O₂(CN₂) was obtained in which a different stacking sequence of yttrium atoms creates a doubling of the c‐axis. Europium‐doped samples of Y₂O₂(CN₂) were prepared and the luminescence properties of Y₂O₂(CN₂):Eu are presented.     

Reaction of (C6F5)2HGeGeH(C6F5)2 with triethylbismuth: molecular structure of [(C6F5)2Ge]4Bi2

The reaction of (C₆F₅)₂HGeGeH(C₆F₅)₂ with triethylbismuth affords a new polynuclear germylbismuth derivative, [(C₆F₅Ge]₄Bi₂ (1). The metal framework of molecule1 has the form of a gable roof built by two central Bi atoms and four peripheral Ge atoms with covalent Bi-Bi bonds [3.045(3) Å], Bi-Ge [2.724(5)-2.755(4) Å] and Ge-Ge [2.444(6), 2.465(6) Å].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 921–924, May, 1994.     

Crystallographic report: Chain‐like crystal structure of [Ni(en)2Ag(CN)2] [Ag(CN)2]

[catena‐Bis(1,2‐diaminoethane)nickel(II)‐µ‐dicyanoargentate]‐dicyanoargentate, [Ni(en)₂Ag₂(CN)₄], was synthesized and its chain‐like crystal structure was determined by X‐ray crystal analysis. Copyright © 2005 John Wiley & Sons, Ltd.     

Crystal and molecular structure of Dicyanotetrasulfane S4(CN)2

S₄(CN)₂ crystallizes in the monoclinic space group P2₁/c with a = 885.7 pm, b = 794.2 pm, c = 1032.6 pm, β = 109.0° (at 173 K). The molecules occupy general sites but are of approximate C₂ symmetry. The conformation of the molecules is all-trans with torsional angles CSSS = 74.6° and 81.7° and SSSS = 84.8°. The central SS bond (201.7 pm) is much shorter than the terminal SS bonds (av. 206.8 pm). There are no stronger than van-der-Waals type intermolecular interactions.     

WCu4S4Cl2(NC5H5)6的合成及晶体结构

(NH_4)_2WS_4,CuCl 和 NH_2OH·HCl 在吡啶溶液中反应可得到红色晶体 WCu_4S_4Cl_2(NC_5H_5)_6.晶体属于单斜晶系,空间群为为 C_(2h)~6-C2/c.晶胞参数为:a=14.883(9),b=12.580(6),c=20.318(9)(?);β=100.50(4)°;Z=4.结构用重原子法解出,经最小二乘法修正,偏离因子R=0.069.分子具有 C_2点群对称性,中心 W 原子以平面四方形形式和四个 Cu 原子结合.W—Cu间平均距离为2.673(?).该化合物为钨铜的混合金属原子簇化合物.     

Synthesis, structure, and magnetic properties of [(CH3CN)5V-O-V(CH3CN)5][BF4]4

The reaction of vanadium(III) acetylacetonate with HBF4 in acetonitrile yields [(CH3CN)5V-O-V(CH3CN)5][BF4]4, a material that serves as a convenient precursor to other [V-O-V]4+ species such as [(bipy)2(CH3CN)V-O-V(CH3CN)(bipy)2][BF4]4 (bipy=2,2'-bipyridine). Single-crystal X-ray diffraction shows that the V-O-V linkage of [(CH3CN)5V-O-V(CH3CN)5]4+ is linear. An Evans method measurement of the solution-phase magnetic susceptibility indicates strong ferromagnetic coupling between the vanadium centers. Magnetic susceptibility (chi) and magnetization (M(H)) data for a powdered sample and for a single crystal oriented with its V-O-V axis parallel to the applied field were measured over 1.8-300 K. The results suggest that the V(III) centers are ferromagnetically coupled with J approximately 72 K (approximately 50 cm(-1)) yielding a ground state with a total spin Stotal=2. Theoretical fit to the M(H) plot for the single crystal yielded g||=2.01+/-0.01 and the zero-field splitting parameter D=0.60+/-0.04 K (0.42+/-0.03 cm(-1)). EPR measurements at 34 and 101.6 GHz are consistent with the Stotal=2 ground state and yield g||=1.9825, g perpendicular=1.9725 and D=0.57+/-0.03 K.     

The transformation of Sn(ND3)2F4 into Sn(ND2)2F2. Synthesis and neutron crystal structure determination of Sn(ND2)2F2

Diamido-difluoro-tin Sn(ND₂)₂F₂ can be produced by ammonolysis from (NH₄)₂SnF₆ at 633 K. The compound is a product formed from Sn(ND₃)₂F₄ during the ammonolysis reaction. Sn(ND₂)₂F₂ isostructural with Sn(NH₂)₂F₂ crystallizes in space group C2/m with lattice constants a = 1072.92(7), b = 325.97(1) pm, c = 505.79(4) pm and β = 105.713(6) ° (V = 170.28(1) ·10⁶ pm³) containing two formula units per unit cell. Data refinement by the Rietveld method of neutron time-of-flight data collected at POLARIS yields a weighted profile R-value R_wp = 0.022. Tin is octahedrally coordinated by two fluorine atoms and four amido groups. The octahedra are connected to one-dimensional chains by edge sharing. The ND₂ groups are in the bridging position whilst the fluorine atoms are terminal. Nearly linear (175.2(4) °) and angular (134.35(8) °) N-D···F hydrogen linkages connect the chains.     

A solid-state spectral effect in eclipsed tetracyanonickelates: X-ray crystal structure, polarized specular reflectance spectroscopy, and ZINDO modeling of Sr[Ni(CN)4].5H2O, Rb2[Ni(CN)4].H2O, and Na2[Ni(CN)4].3H2O

Crystal structures of three Ni(CN)(4)(2)(-) salts all with eclipsed ligands and varying axial stacking arrangements are presented. The absorption spectra of all three salts show a slight red shift in the x,y-polarizations and a large red shift in their z-polarizations upon crystallization from solution. Semiempirical ZINDO calculations provide a good model of the solid state, even with only a three-molecule segment, allowing reproduction of the red-shifting and intensity increase upon crystallization found experimentally. The modified nickel beta(s,p) bonding parameter of -5 found appropriate for Ni coordination in our previous studies of single Ni(CN)(4)(2-) planes and a helically stacked Cs(2)[Ni(CN)(4)].H(2)O crystal was changed to -3 for the more parallel-stacked Ni(CN)(4)(2-) planes in this case, while beta(d) was retained at -41. Crystal data are as follows: Na(2)[Ni(CN)(4)].3H(2)O, triclinic space group P1, a = 7.2980(10) A, b = 8.8620(10) A, c = 15.132(2) A, alpha = 89.311(5) degrees, beta = 87.326(5) degrees, gamma = 83.772(6) degrees, V = 971.8(2) A(3), T = 100 K, Z = 4, R = 0.024, R(w) = 0.064; Sr[Ni(CN)(4)].5H(2)O, monoclinic space group C2/m, a = 10.356(2) A, b = 15.272(3) A, c = 7.1331(10) A, beta = 98.548(12) degrees, V = 1115.6(3) A(3), T = 100 K, Z = 4, R = 0.024, R(w) = 0.059; Rb(2)[Ni(CN)(4)].1.05H(2)O, triclinic space group P1, a = 8.6020(10) A, b = 9.6930(10) A, c = 12.006(2) A, alpha = 92.621(6) degrees, beta = 94.263(6) degrees, gamma = 111.795(10) degrees, V = 924.0(2) A(3), T = 100 K, Z = 4, R = 0.034, R(w) = 0.067.